CN114289067B - Binary metal catalyst, preparation method and application thereof - Google Patents
Binary metal catalyst, preparation method and application thereof Download PDFInfo
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- CN114289067B CN114289067B CN202111656009.4A CN202111656009A CN114289067B CN 114289067 B CN114289067 B CN 114289067B CN 202111656009 A CN202111656009 A CN 202111656009A CN 114289067 B CN114289067 B CN 114289067B
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- metal catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 74
- 239000002184 metal Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 237
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 35
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 120
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 105
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 74
- 150000001875 compounds Chemical class 0.000 claims description 73
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 60
- -1 C 3-12 Cycloalkyl radical Chemical class 0.000 claims description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 230000015572 biosynthetic process Effects 0.000 claims description 38
- 239000011734 sodium Substances 0.000 claims description 38
- 238000003786 synthesis reaction Methods 0.000 claims description 36
- 239000000460 chlorine Substances 0.000 claims description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 150000008282 halocarbons Chemical class 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 3
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 125000001831 (C6-C10) heteroaryl group Chemical group 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 2
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052806 inorganic carbonate Inorganic materials 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 229910052987 metal hydride Inorganic materials 0.000 claims description 2
- 150000004681 metal hydrides Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002577 pseudohalo group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- ITNMDRWLTGIOCF-UHFFFAOYSA-N 2-ethoxy-3-methoxyphenol Chemical compound CCOC1=C(O)C=CC=C1OC ITNMDRWLTGIOCF-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims 1
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims 1
- ALRHLSYJTWAHJZ-UHFFFAOYSA-M 3-hydroxypropionate Chemical compound OCCC([O-])=O ALRHLSYJTWAHJZ-UHFFFAOYSA-M 0.000 abstract description 76
- 239000000203 mixture Substances 0.000 description 74
- 238000003756 stirring Methods 0.000 description 64
- 239000012298 atmosphere Substances 0.000 description 60
- 238000005406 washing Methods 0.000 description 60
- 238000004817 gas chromatography Methods 0.000 description 53
- 239000010948 rhodium Substances 0.000 description 42
- 239000002904 solvent Substances 0.000 description 41
- 239000003446 ligand Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 35
- 238000006555 catalytic reaction Methods 0.000 description 32
- 229910000831 Steel Inorganic materials 0.000 description 30
- 239000000654 additive Substances 0.000 description 30
- 230000000996 additive effect Effects 0.000 description 30
- 238000000921 elemental analysis Methods 0.000 description 30
- 239000000706 filtrate Substances 0.000 description 30
- 238000001914 filtration Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 30
- 238000002347 injection Methods 0.000 description 30
- 239000007924 injection Substances 0.000 description 30
- 239000012299 nitrogen atmosphere Substances 0.000 description 30
- 239000010959 steel Substances 0.000 description 30
- 238000005303 weighing Methods 0.000 description 30
- 239000011541 reaction mixture Substances 0.000 description 18
- SUCYXRASDBOYGB-UHFFFAOYSA-N cobalt rhodium Chemical compound [Co].[Rh] SUCYXRASDBOYGB-UHFFFAOYSA-N 0.000 description 16
- 150000003284 rhodium compounds Chemical class 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910007926 ZrCl Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- RVGLEPQPVDUSOJ-UHFFFAOYSA-N 2-Methyl-3-hydroxypropanoate Chemical compound COC(=O)CCO RVGLEPQPVDUSOJ-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940017219 methyl propionate Drugs 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical compound [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- AXTNPHLCOKUMDY-UHFFFAOYSA-N chromium cobalt Chemical compound [Co][Cr][Co] AXTNPHLCOKUMDY-UHFFFAOYSA-N 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 2
- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 description 2
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 2
- GNEMDYVJKXMKCS-UHFFFAOYSA-N cobalt zirconium Chemical compound [Co].[Zr] GNEMDYVJKXMKCS-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002604 lanthanum compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical class OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- MDKXFHZSHLHFLN-UHFFFAOYSA-N alumanylidynecobalt Chemical compound [Al].[Co] MDKXFHZSHLHFLN-UHFFFAOYSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000000937 inactivator Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a binary metal catalyst [ (C) 5 H 4 N‑2‑CH＝N‑R) m ML n ] + [Co(CO) 4 ] ‑ (m =1,2) and a process for preparing the same, and also provides a process for preparing 3-hydroxypropionate by catalyzing the reaction of alkylene oxide, carbon monoxide and organic alcohol using the catalyst. The binary metal catalyst is used for catalyzing and preparing the 3-hydroxy propionate, and has high conversion rate of alkylene oxide and selectivity of the 3-hydroxy propionate.
Description
Technical Field
The invention relates to the field of catalytic preparation of 3-hydroxy propionate, and in particular relates to a binary metal catalyst, a preparation method and application thereof.
Background
The 3-hydroxy propionate is an important bacterial inactivator and is also a raw material monomer for synthesizing the polypropiolactone. The current widespread use of 3-hydroxypropionates is in the synthesis of 1, 3-propanediol. 1, 3-propanediol has important applications in antifreeze, plasticizer, detergent, preservative and emulsifier, and is also an important intermediate for the synthesis of various drugs and organic molecules, and an important monomer for novel polyester materials, polytrimethylene terephthalate and novel polyurethane materials. 1, 3-propanediol is a hotspot product in current research and development, and 3-hydroxy propionate is an important research and development raw material.
The methods for synthesizing the methyl 3-hydroxypropionate are not reported in many ways, and the current mainstream process is to synthesize the 3-hydroxypropionate by ethylene oxide hydrogen esterification reaction, namely, the 3-hydroxypropionate is synthesized by reacting ethylene oxide and CO which are used as raw materials with organic alcohol under the action of a catalyst.
The domestic research conditions are as follows: in 2006, the method for preparing 3-methyl hydroxypropionate, which is developed by Chenjing et al, national institute of science and chemistry and physics, of Lanzhou, takes transition metal cobalt as a catalyst, ethylene oxide and CO as raw materials, methanol or ethanol as a solvent, the reaction temperature is 70-75 ℃, the CO pressure is 8-10 MPa, the reaction is carried out for 3-5 hours, and the selectivity of the 3-methyl hydroxypropionate can reach 98% (CN 101020635A). In 2010, chenxiaoping et al, guangdong institute of petrochemical engineering 2 (CO) 8 As a catalyst, epoxyethane and CO are used as reactants, methanol is used as a solvent, supercritical carbon dioxide is used as a reaction medium, and the methyl 3-hydroxypropionate is synthesized under the conditions that the pressure is 11-20 MPa, the temperature is 35-95 ℃ and the reaction time is 22-26 hours. The conversion rate of the epoxy ethane is between 93.32 and 99.56 percent, and the selectivity of the methyl 3-hydroxypropionate is between 59.76 and 92.91 percent. From 2012 to 2014, fangning et al, yangzhou chemical research institute of Nanjing university, registered as Na [ Co (CO) 4 ]The catalyst takes 1,4 '-butanediyl-3, 3' -bis-1-vinylimidazole dibromide as an auxiliary agent, and reacts for 5 hours at 75 ℃ and under the CO pressure of 2MPa, wherein the conversion rate of ethylene oxide is 41.8-47.7%, and the selectivity is 87.0-96.2% (105272855A); wangyining et al Co 2 (CO) 8 Pyridine, pyrimidine, imidazole or purine is used as a catalyst, and the reaction is carried out for 5 hours at 75 ℃ and CO pressure of 2MPa, wherein the conversion rate of the epoxy ethane is 62.1-91.2%, and the selectivity is 43.7-83.2% (CN 107417527A). Liubo et al, 2014 to 2018 by reacting an ionic liquid with CoCl 2 Reaction to produce a catalyst containing Co 3+ The liquid catalyst reacts for 5 to 12 hours under the conditions that the CO pressure is 3 to 8MPa, the reaction temperature is 45 to 100 ℃, the conversion rate of the ethylene oxide is 58 to 95 percent, and the selectivity of the 3-hydroxy methyl propionate can reach 86 percent (CN 107459451). Similarly, cu-containing compounds are formed by reacting ionic liquids with CuCl 2+ The liquid catalyst has CO pressure of 3-8 MPa, reaction temperature of 45-100 deg.c, reaction time of 3-8 hr, ethylene oxide conversion rate up to 95% and methyl 3-hydroxypropionate selectivity up to 83% (CN 107459452). The Liubo et al later use ionic liquid and FeCl 3 Or cuprous halide is used for preparing a catalyst, the reaction is carried out for 3 to 10 hours at the temperature of between 50 and 80 ℃ and under the pressure of between 3 and 10MPa, the conversion rate of the ethylene oxide can reach 99 percent, and the selectivity of the 3-hydroxy methyl propionate can reach 94 percent (CN 109678710). Meanwhile, a noble metal ruthenium complex catalyst is disclosed, and the reaction is carried out for 2-6 hours under the conditions that the CO pressure is 2-5 MPa, the reaction temperature is 45-65 ℃, the conversion rate of the ethylene oxide is 80-99 percent, and the selectivity of the 3-hydroxy methyl propionate can reach 97 percent (CN 109678709).
These results show that the selection of a suitable catalyst and the control of the corresponding reaction conditions are important for the conversion of ethylene oxide and the selectivity of the formation of 3-hydroxypropionate. It has also been found that controlling the high conversion of ethylene oxide and the high selectivity of formation of 3-hydroxypropionate remains a problem to be solved in the art, and the key to solving this problem is the catalyst.
Disclosure of Invention
The first purpose of the invention is to provide a binary metal catalyst for catalyzing and preparing 3-hydroxy propionate. The second object of the present invention is to provide a method for preparing the above binary metal catalyst. The third purpose of the invention is to provide the application of the binary metal catalyst in the catalytic preparation of 3-hydroxy propionate. The fourth purpose of the invention is to provide a preparation method of 3-hydroxy propionate.
To achieve the above object, a first aspect of the present invention provides a binary metal catalyst represented by [ (C) 5 H 4 N-2-CH＝NR) m ML n ] + [Co(CO) 4 ] - Wherein m =1 or 2;
when m =2, the binary metal catalyst has a structure represented by general formula (A),
when m =1, the binary metal catalyst has a structure represented by general formula (B),
wherein M is a main group metal, a transition metal or a lanthanide metal, and M is not Co;
each R is independently selected from C 1-12 Straight or branched alkyl, C 1-12 Heteroalkyl group, C 3-12 Cycloalkyl, C 3-12 Heterocycloalkyl or C 6-10 Aryl, wherein said C 1-12 Straight or branched alkyl, C 1-12 Heteroalkyl group, C 3-12 Cycloalkyl, C 3-12 Heterocycloalkyl or C 6-10 Aryl being optionally substituted by halogen, hydroxy, amino, cyano, C 1-6 Alkyl radical, C 1-6 At least one of alkoxy groups is mono-or poly-substituted;
l is selected from hydrogen, -C = O, halogen, pseudohalogen, C 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 1-6 Alkanemercapto group, C 6-10 Aryl radical, C 6-10 Heteroaryl, amino, hydroxy, C 1-6 Carboxyl group, sulfonic acid group, C 1-6 Alkylsulfonic acid group, or acetylacetonato group, wherein said C 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 1-6 Alkanemercapto group, C 6-10 Aryl, amino, C 1-6 Carboxyl group, sulfonic acid group, C 1-6 Alkylsulfonic acid group, acetylacetone group optionally substituted by halogen, hydroxy, cyano, C 1-6 Alkyl radical, C 1-6 At least one of alkoxy, amino and trimethylsilyl is mono-substituted or polysubstituted;
n represents the number of L and is an integer of 0 to 3.
The binary metal catalyst provided by the invention is a cathodeA cation pair compound. Wherein the general formula (A) is represented by [ (C) 5 H 4 N-2-CH＝NR) 2 ML n ] + [Co(CO) 4 ] - The anionic moiety being [ Co (CO) 4 ] - The cation is a complex of a metal M, and in the general formula (A), R is a substituent on an amino group, and each R may be the same or different. In the cationic moiety, the ligand is a pyridimine ligand, the N atom of which is chemically bonded to the central metal M, and L represents a group to which M is bonded except for the dinitrogen ligand. The general formula (B) is represented by [ (C) 5 H 4 N-2-CH＝NR)ML n ] + [Co(CO) 4 ] - The anionic moiety being [ Co (CO) 4 ] - The cation is a complex of a metal M, and in the formula (B), R is a substituent on the amino group. In the cationic moiety, the ligand is a pyridimine ligand, the N atom of which is chemically bonded to the central metal M, and L represents a group to which M is bonded except for the dinitrogen ligand.
In some embodiments of the first aspect of the present invention, each R is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diisopropylphenyl, 2, 6-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, 2,4, 6-triisopropylphenyl, 2,4, 6-tri-tert-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, thienyl.
In some embodiments of the first aspect of the present invention, M is selected from Mn, ga, sr, ba, al, ga, in, sn, ge, sc, ti, V, cr, mn, fe, ni, cu, zn, Y, zr, nb, mo, la, pr, ce, nd, sm, eu, gd, dy, er, yb, lu, rh.
In some embodiments of the first aspect of the present invention, L is selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, methyl, ethyl, butyl, trimethylsilylmethyl, phenyl, benzyl, methoxy, ethoxy, phenolic, formic, acetic, dimethylamino, diethylamino, diisopropylamino, di-t-butylamino, di (trimethylsilyl) amino, acetylacetonate, hydroxy, sulfonic, methylsulfonic, and trifluoromethylsulfonic.
In some embodiments of the first aspect of the present invention, in formula (a), both R are the same and are selected from tert-butyl, isopropyl; m is selected from Rh, mn, la and Cr; l is selected from chlorine or is absent; n is 0, 1 or 2. In the general formula (B), R is selected from tert-butyl and isopropyl; m is selected from Rh, mn and La; l is selected from chlorine or-C = O; n is 1 or 2.
In some embodiments of the first aspect of the present invention, the binary metal catalyst is selected from the group consisting of:
a second aspect of the present invention provides a preparation method of the foregoing binary metal catalyst, including:
reacting compound (C) 5 H 4 N-2-CH＝NR) m ML n+1 And Na [ Co (CO) 4 ]And (3) reacting in a first organic solvent to remove LNa, thereby obtaining the binary metal catalyst. Wherein M, n, M, R, L are each as defined for a compound of formula (A) or formula (B) of the first aspect of the invention.
In some embodiments of the second aspect of the present invention, the first organic solvent is selected from at least one of alkanes, aromatic hydrocarbons, heterocyclic alkanes, halogenated hydrocarbons, ethers, amines; preferably, the first organic solvent is selected from at least one of benzene, toluene, xylene, tetrahydrofuran, diethyl ether, hexane, heptane, chloroform, dichloromethane, triethylamine, and methylphenylamine.
In some embodiments, the substrate Na [ Co (CO) ] 4 ]Can be synthesized by referring to the literature (Journal of Organometallic Chemistry,2017,133, 849).
In some embodiments, the substrate (C) used for the synthesis of the compound of formula (A) 5 H 4 N-2-CH＝NR) 2 ML n+1 2-4 times of ligand compound C can pass through 5 H 4 N-2-CH = NR and metal compound ML n+1 In a solvent, wherein the 2-4 times of the amount of the C is C 5 H 4 Molar number of N-2-CH = NR is ML n+1 2-4 times of the mole number of the medium metal M.
In other embodiments, the substrate (C) used to synthesize the compound of formula (B) 5 H 4 N-2-CH＝NR)ML n+1 1-2 times of the ligand compound C can be passed 5 H 4 N-2-CH = NR and metal compound ML n+1 In a solvent, wherein the 1-2 times of the amount of the C is C 5 H 4 The number of moles of N-2-CH = NR is ML n+1 1-2 times of the mole number of the medium metal M.
Synthesis of (C) 5 H 4 N-2-CH＝NR) 2 ML n+1 And (C) 5 H 4 N-2-CH＝NR)ML n+1 The solvent used may be selected from conventional solvents selected from alkanes, aromatic hydrocarbons, halogenated hydrocarbons, ethers, amines, preferably from benzene, toluene, xylene, tetrahydrofuran, diethyl ether, hexane, heptane, chloroform, dichloromethane, triethylamine, methylphenylamine.
In a third aspect, the invention provides an application of the binary metal catalyst in the catalytic preparation of 3-hydroxy propionate.
In some embodiments of the third aspect of the present invention, a previously synthesized compound of formula (a) or (B) may be used directly in the catalytic reaction.
In other embodiments of the third aspect of the present invention, (C) capable of forming a compound of formula (A) 5 H 4 N-2-CH＝NR) 2 ML n+1 And Na [ Co (CO) 4 ]Adding the catalyst into a catalytic reaction system to form a catalyst with a general formula (A) in situ for catalysis; or,(C) which may be used to form a compound of the formula (B) 5 H 4 N-2-CH＝NR)ML n+1 And Na [ Co (CO) 4 ]Adding the catalyst into a catalytic reaction system to form the catalyst with the general formula (B) in situ for catalysis.
The fourth aspect of the present invention provides a method for preparing 3-hydroxypropionate, which comprises the following steps: reacting a reaction system comprising the aforementioned bimetallic catalyst, an auxiliary, an alkylene oxide, carbon monoxide, an organic alcohol, and optionally a second organic solvent to produce a 3-hydroxypropionate.
Wherein the binary metal catalyst is prepared from a compound (C) 5 H 4 N-2-CH＝NR) m ML n+1 And Na [ Co (CO) 4 ]In-situ reaction in a reaction system or pre-synthesis; the auxiliary agent is an alkaline substance.
In the invention, the catalytic preparation of the 3-hydroxy-propionate has good catalytic effect when an auxiliary agent is added, and the mole number of the auxiliary agent is 0.01-10% of that of the catalyst. The auxiliary agent is an alkaline substance which regulates the alkalescence of the reaction system (for example, pH 7.5-9) and converts or promotes ML (ML) n The reactivity of (a).
In some embodiments of the fourth aspect of the present invention, the adjuvant is selected from the group consisting of inorganic carbonates, main group metal salts of organic alcohols or phenols or carboxylic acids, main group metal amine compounds, main group metal alkoxide compounds, main group metal hydrides. Preferably, the auxiliary agent is at least one selected from sodium carbonate, potassium carbonate, sodium bicarbonate, sodium ethoxide, sodium phenolate, sodium acetate, diethylamine, triethylamine and diethanolamine.
In some embodiments of the fourth aspect of the invention, the catalytic production reaction involves the starting materials alkylene oxide, carbon monoxide and an organic alcohol, and may be carried out in the corresponding organic alcohol, where the organic alcohol is both the starting material and the solvent for the reaction. The organic alcohol is selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, and benzyl alcohol, preferably from methanol, ethanol, propanol, butanol, cyclopentanol, and cyclohexanol.
In other embodiments of the fourth aspect of the present invention, the reaction system may further comprise a second organic solvent. The second organic solvent is selected from one of alkane, ether, tetrahydrofuran, 2, 6-oxygen ring, aromatic solvent and halogenated hydrocarbon, preferably one of pentane, hexane, cyclohexane, diethyl ether, tetrahydrofuran, benzene, toluene and dichloromethane.
In some embodiments of the fourth aspect of the present invention, the reaction conditions are as follows: the reaction temperature is 0-250 ℃, and preferably 20-150 ℃; the reaction pressure is 0.1-60 MPa, preferably 0.1-20 MPa; the reaction time is 1-50 hours, the reaction time depends on the concentration of the catalyst, and the higher the concentration of the catalyst is, the shorter the reaction time is; conversely, the lower the catalyst concentration, the longer the reaction time. In some embodiments, the molar ratio of the binary metal catalyst to alkylene oxide is (0.5-5): 100, preferably (0.8-1.2): 100.
The catalytic preparation reaction provided by the present invention is effective not only on ethylene oxide but also on other alkylene oxides than ethylene oxide, and in some embodiments, the alkylene oxide is preferably selected from ethylene oxide, propylene oxide, butylene oxide, and cyclohexene oxide.
In other embodiments of the fourth aspect of the present invention, the catalytic reaction may be performed in a reactor, and the reactor may be selected from one of a tank type, a tower type and a pipe type.
The binary metal catalyst provided by the invention can catalyze the reaction of ethylene oxide, carbon monoxide and organic alcohol to generate 3-hydroxy propionate, and has high conversion rate of ethylene oxide and selectivity of 3-hydroxy propionate.
In addition, the binary metal catalyst provided by the invention has very excellent catalytic effect when ethylene oxide is used as a substrate, and has excellent catalytic effect when other alkylene oxides are used as substrates.
Drawings
FIG. 1 is a gas chromatogram of a 3-hydroxypropionate prepared in twenty-six example,
FIG. 2 is a gas chromatogram of 3-hydroxypropionate prepared in example forty-six.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the following. In the following examples, those not indicated with specific conditions were performed according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example one
(1) Synthesis of rhodium cobalt binary metal catalyst compound XMC-1 (done under inert atmosphere).
Weighing four times of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr) 2 RhCl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with n-hexane to obtain the compound XMC-1 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr) 2 Rh] + [Co(CO) 4 ] - The yield was 85%. Elemental analysis confirmed composition, theoretical value: 46.33% of C, 4.24% of H and 9.82% of N; experimental values: 46.35% of C, 4.21% of H and 9.80% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-1 as catalyst (reaction is completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle for N 2 After washing, sequentially adding XMC-1 1mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction is finished, quickly cooling the reaction kettle to 0 ℃, slowly releasing the pressure to normal pressure, and extracting the reaction liquidGas chromatography was performed and the results are reported in table 1.
Example two
(1) The synthesis of rhodium cobalt binary metal catalyst compound XMC-2 (done under inert atmosphere).
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr)Rh(CO) 2 And (4) Cl. Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-2 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr)Rh(CO) 2 ] + [Co(CO) 4 ] - The yield was 85%. Elemental analysis confirmed the composition, theoretical values: c37.68%, H2.53%, N5.86%; experimental values: 38.01 percent of C, 2.51 percent of H and 5.80 percent of N.
(2) Preparation of 3-hydroxy propionate by using XMC-2 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-2 1mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
EXAMPLE III
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-3 (done under inert atmosphere)
Weighing four times of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NEt and rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NEt) 2 RhCl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with n-hexane to obtain the compound XMC-3 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NEt) 2 Rh] + [Co(CO) 4 ] - The yield was 86%. Elemental analysis confirmed the composition, theoretical values: 44.30% of C, 3.72% of H and 10.33% of N; experimental values: 44.32% of C, 3.70% of H and 10.33% of N.
(2) Catalytic preparation of 3-hydroxypropionate using XMC-3 as catalyst (the reaction is completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-3 1mmol, triethylamine additive 0.03mmol, ethylene Oxide (EO) 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and gas chromatography was performed, and the results are recorded in table 1.
Example four
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-4 (done under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NEt and rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NEt)Rh(CO) 2 And (4) Cl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reaction is 8 hoursFiltering to collect filtrate, removing solvent under reduced pressure, and washing with n-hexane to obtain compound XMC-4 with molecular formula of [ (C) 5 H 4 N-2-CH＝NEt)Rh(CO) 2 ] + [Co(CO) 4 ] - The yield was 86%. Elemental analysis confirmed the composition, theoretical values: 36.23% of C, 2.17% of H and 6.04% of N; experimental values: 36.92% of C, 2.50% of H and 6.41% of N.
(2) Catalytic preparation of 3-hydroxypropionate using XMC-4 as catalyst (the reaction is completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-4 1mmol, triethylamine additive 0.03mmol, ethylene Oxide (EO) 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
EXAMPLE five
(1) The synthesis of rhodium cobalt binary metal catalyst compound XMC-5 (done under inert atmosphere).
Weighing four times of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NtBu and rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NtBu) 2 RhCl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with n-hexane to obtain the compound XMC-5 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NtBu) 2 Rh] + [Co(CO) 4 ] - The yield was 75%. Elemental analysis confirmed the composition, theoretical values: 48.18% of C, 4.72% of H and 9.36% of N; experimental values: 48.15% of C, 4.75% of H and 9.35% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-5 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-5 1mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
Example six
(1) The synthesis of rhodium cobalt binary metal catalyst compound XMC-6 (done under inert atmosphere).
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NtBu and rhodium compound Rh 2 Cl 2 (CO) 4 Placing in a Schlenk bottle, adding a toluene solvent, and stirring at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NtBu)Rh(CO) 2 And (4) Cl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-6 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NtBu)Rh(CO) 2 ] + [Co(CO) 4 ] - The yield was 75%. Elemental analysis confirmed composition, theoretical value: 39.05% of C, 2.87% of H and 5.69% of N; experimental values: 39.76% of C, 2.95% of H and 6.05% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-6 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, XMC-6 is added in sequence1mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing the sample injection valve, connecting the carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
EXAMPLE seven
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-7 (done under inert atmosphere)
Weighing four times of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NnBu and rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NnBu) 2 RhCl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-7 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NnBu) 2 Rh] + [Co(CO) 4 ] - The yield was 82%. Elemental analysis confirmed the composition, theoretical values: 48.18 percent of C, 4.72 percent of H and 9.36 percent of N; experimental values: 48.20% of C, 4.76% of H and 9.38% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-7 as catalyst (reaction is completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-7 1mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and gas chromatography was performed, and the results are recorded in table 1.
Example eight
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-8 (done under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NnBu and rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NnBu)Rh(CO) 2 And (4) Cl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with n-hexane to obtain a compound XMC-8 with a molecular formula of [ (C) 5 H 4 N-2-CH＝NnBu)Rh(CO) 2 ] + [Co(CO) 4 ] - The yield was 82%. Elemental analysis confirmed the composition, theoretical values: 39.05% of C, 2.87% of H and 5.69% of N; experimental values: 39.90% of C, 2.96% of H and 6.03% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-8 as catalyst (reaction is completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-8 1mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and gas chromatography was performed, and the results are recorded in table 1.
Example nine
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-9 (done under inert atmosphere)
Weighing four times of ligand C in nitrogen atmosphere 5 H 4 N-2-CH＝NnC 5 H 9 And rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NnC 5 H 9 ) 2 RhCl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with n-hexane to obtain the compound XMC-9 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NnC 5 H 9 ) 2 Rh] + [Co(CO) 4 ] - The yield was 74%. Elemental analysis confirmed composition, theoretical value: 49.85% of C, 5.15% of H and 8.94% of N; experimental values: 49.81% of C, 5.16% of H and 9.00% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-9 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle for N 2 After washing, sequentially adding XMC-9 1mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
Example ten
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-10 (done under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH＝NnC 5 H 9 And rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NnC 5 H 9 )Rh(CO) 2 And (4) Cl. Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-10 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NnC 5 H 9 )Rh(CO) 2 ] + [Co(CO) 4 ] - Yield 74%. Elemental analysis confirmed the composition, theoretical values: 40.34% of C, 3.19% of H and 5.53% of N; experimental values: 40.99% of C, 3.36% of H and 5.84% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-10 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-10 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and gas chromatography was performed, and the results are recorded in table 1.
EXAMPLE eleven
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-11 (done under inert atmosphere)
Weighing four times of ligand C in nitrogen atmosphere 5 H 4 N-2-CH＝N-cyclo-C 6 H 11 And rhodium compound Rh 2 Cl 2 (CO) 4 Placing in a Schlenk bottle, adding a toluene solvent, and stirring at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝N-cyclo-C 6 H 11 ) 2 RhCl. Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-11 with a molecule of [ (C) 5 H 4 N-2-CH＝N-cyclo-C 6 H 11 ) 2 Rh] + [Co(CO) 4 ] - The yield was 82%. Elemental analysis confirmed composition, theoretical value:c51.71%, H4.96%, N8.61%; experimental values: c51.70%, H4.99%, N8.63%.
(2) Preparation of 3-hydroxy propionate by using XMC-11 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-11 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
Example twelve
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-12 (done under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH＝N-cyclo-C 6 H 11 And rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝N-cyclo-C 6 H 11 )Rh(CO) 2 And (4) Cl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-12 with a molecule of [ (C) 5 H 4 N-2-CH＝N-cyclo-C 6 H 11 )Rh(CO) 2 ] + [Co(CO) 4 ] - The yield was 82%. Elemental analysis confirmed composition, theoretical value: 41.72 percent of C, 3.11 percent of H and 5.41 percent of N; experimental values: 42.57% of C, 3.49% of H and 5.87% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-12 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-12 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
EXAMPLE thirteen
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-13 (completed under inert atmosphere)
Weighing four times of ligand C in nitrogen atmosphere 5 H 4 N-2-CH＝NC 6 H 5 And rhodium compound Rh 2 Cl 2 (CO) 4 Placing in a Schlenk bottle, adding a toluene solvent, and stirring at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NC 6 H 5 ) 2 RhCl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing solvent under reduced pressure and washing with n-hexane to obtain compound XMC-13 with molecular formula [ (C) 5 H 4 N-2-CH＝NC 6 H 5 ) 2 Rh] + [Co(CO) 4 ] - The yield was 91%. Elemental analysis confirmed the composition, theoretical values: 52.69% of C, 3.16% of H and 8.78% of N; experimental values: 52.71% of C, 3.20% of H and 8.77% of N.
Preparation of 3-hydroxy propionate by using XMC-13 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle for N 2 After washing, sequentially adding XMC-13 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction is finished, quickly cooling the reaction kettle to 0 ℃, slowly releasing the pressure to normal pressure, and extracting the reaction liquidGas chromatography was performed and the results are reported in table 1.
Example fourteen
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-14 (completed under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH＝NC 6 H 5 And rhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NC 6 H 5 )Rh(CO) 2 And (4) Cl. Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with n-hexane to obtain the compound XMC-14 with the molecular formula [ (C) 5 H 4 N-2-CH＝NC 6 H 5 )Rh(CO) 2 ] + [Co(CO) 4 ] - The yield was 91%. Elemental analysis confirmed the composition, theoretical values: c42.22%, H1.97%, N5.47%; experimental values: c42.77%, H2.15%, N5.95%.
(2) Preparation of 3-hydroxy propionate by using XMC-14 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle for N 2 After washing, sequentially adding XMC-14 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
Example fifteen
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-15 (completed under inert atmosphere)
Weighing four times of ligand C in nitrogen atmosphere 5 H 4 N-2-CH＝N-(2,4,6-Me 3 C 6 H 2 ) And rhodium compound Rh 2 Cl 2 (CO) 4 Placing in a Schlenk bottle, adding toluene solvent, stirring at room temperature for 12 hours to obtain [ C 5 H 4 N-2-CH＝N-(2,4,6-Me 3 C 6 H 2 )] 2 RhCl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-15 with the molecular formula { [ C ] 5 H 4 N-2-CH＝N-(2,4,6-Me 3 C 6 H 2 )] 2 Rh} + [Co(CO) 4 ] - The yield was 79%. Elemental analysis confirmed composition, theoretical value: 52.52% of C, 4.46% of H and 7.75% of N; experimental values: c52.54%, H4.42%, N7.77%.
(2) Preparation of 3-hydroxy propionate by using XMC-15 as catalyst (reaction is completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-15 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
Example sixteen
(1) Synthesis of rhodium cobalt binary Metal catalyst Compound XMC-16 (completed under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH＝N-(2,4,6-Me 3 C 6 H 2 ) Andrhodium compound Rh 2 Cl 2 (CO) 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain [ C 5 H 4 N-2-CH＝N-(2,4,6-Me 3 C 6 H 2 )]Rh(CO) 2 And (4) Cl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-16 with the molecular formula { [ C ] 5 H 4 N-2-CH＝N-(2,4,6-Me 3 C 6 H 2 )]Rh(CO) 2 } + [Co(CO) 4 ] - The yield was 79%. Elemental analysis confirmed composition, theoretical value: 45.51% of C, 2.91% of H and 5.05% of N; experimental values: 46.14 percent of C, 3.03 percent of H and 5.34 percent of N.
(2) Preparation of 3-hydroxy propionate by using XMC-16 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-16 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 1.
Table 1: summary of catalytic results for examples one through sixteen
1mmol of catalyst; 0.03mmol of auxiliary agent; ethylene oxide EO 100mmol; 30mL of solvent; the stirring rate was 800rpm.
Example seventeen
(1) Synthesis of chromium cobalt binary Metal catalyst Compound XMC-17 (done under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and chromium compound CrCl 2 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr) 2 CrCl 2 . Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-17 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr) 2 CrCl] + [Co(CO) 4 ] - The yield was 88%. Elemental analysis confirmed the composition, theoretical values: 47.63% of C, 4.36% of H and 10.10% of N; experimental values: 47.63% of C, 4.32% of H and 10.08% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-17 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-17 1mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results were recorded in table 2.
EXAMPLE eighteen
(1) Synthesis of chromium cobalt binary Metal catalyst Compound XMC-18 (done under inert atmosphere)
Weighing a certain amount of ligand C in a nitrogen atmosphere 5 H 4 N-2-CH = NiPr and chromium compound CrCl 2 Placing in a Schlenk bottle, adding a toluene solvent, and stirring at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr)CrCl 2 . Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-18 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr)CrCl] + [Co(CO) 4 ] - The yield was 88%. Elemental analysis confirmed composition, theoretical value: 38.40% of C, 2.97% of H and 6.89% of N; experimental values: 39.13% of C, 3.11% of H and 7.58% of N.
(2) Preparation of 3-hydroxy propionate by catalysis of XMC-18 as catalyst (the reaction is completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle for N 2 After washing, sequentially adding XMC-18 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results were recorded in table 2.
Example nineteen
(1) Synthesis of aluminum cobalt binary Metal catalyst Compound XMC-19 (done under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and aluminum compound Al (Et) 2 Placing Cl in a Schlenk bottle, adding a toluene solvent, and stirring at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr) 2 And (4) AlCl. Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with n-hexane to obtain the compound XMC-19 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr) 2 Al] + [Co(CO) 4 ] - The yield was 93%. Elemental analysis confirmed composition, theoretical value: 53.45% of C, 4.89% of H and 11.33% of N; experimental values: c53.43%, H4.84%, N11.32%.
(2) Preparation of 3-hydroxy propionate by using XMC-19 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-19 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 2.
Example twenty
(1) Synthesis of AlCoCo binary Metal catalyst Compound XMC-20 (done under inert atmosphere)
Weighing a certain amount of ligand C in a nitrogen atmosphere 5 H 4 N-2-CH = NiPr and aluminum compound Al (Et) 2 Placing Cl into a Schlenk bottle, adding a toluene solvent, and stirring at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH = NiPr) Al (Et) Cl. Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-20 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr)AlEt] + [Co(CO) 4 ] - The yield was 93%. Elemental analysis confirmed composition, theoretical value: 48.02% of C, 4.57% of H and 7.47% of N; experimental values: 48.87% of C, 4.76% of H and 7.97% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-20 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-20 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 2.
Example twenty one
(1) Synthesis of ruthenium cobalt binary Metal catalyst Compound XMC-21 (completed under inert atmosphere)
Weighing four times of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and ruthenium compound Ru 2 Cl 2 (CO) 6 Placing in a Schlenk bottle, adding a toluene solvent, and stirring at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr) 2 RuCl. Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with n-hexane to obtain the compound XMC-21 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr) 2 Ru] + [Co(CO) 4 ] - The yield was 90%. Elemental analysis confirmed composition, theoretical value: 46.48% of C, 4.26% of H and 9.86% of N; experimental values: 46.49% of C, 4.30% of H and 9.87% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-21 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle for N 2 After washing, sequentially adding XMC-21 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results were recorded in table 2.
Example twenty two
(1) Synthesis of ruthenium cobalt binary Metal catalyst Compound XMC-22 (done under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and ruthenium compound Ru 2 Cl 2 (CO) 6 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr)Ru(CO) 2 And (4) Cl. Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-22 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr)Ru(CO) 2 ] + [Co(CO) 4 ] - The yield was 90%. Elemental analysis confirmed the composition, theoretical values: 37.83% of C, 2.54% of H and 5.88% of N; experimental values: 38.59% of C, 2.83% of H and 6.27% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-22 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle for N 2 After washing, sequentially adding XMC-22 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 2.
Example twenty three
(1) Synthesis of titanium cobalt binary Metal catalyst Compound XMC-23 (completed under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and titanium compound TiCl 3 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr) 2 TiCl 3 . Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-23 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr) 2 TiCl 2 ] + [Co(CO) 4 ] - The yield was 78%. Elemental analysis confirmed the composition, theoretical values: 45.08% of C, 4.13% of H and 9.56% of N; experimental values: 45.03% of C, 4.16% of H and 9.56% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-23 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-23 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 2.
Example twenty-four
(1) Synthesis of titanium cobalt binary Metal catalyst Compound XMC-24 (completed under inert atmosphere)
Weighing a certain amount of ligand C in a nitrogen atmosphere 5 H 4 N-2-CH = NiPr and titanium compound TiCl 3 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr)TiCl 3 . Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-24, molecular formula is [ (C) 5 H 4 N-2-CH＝NiPr)TiCl 2 ] + [Co(CO) 4 ] - The yield was 78%. Elemental analysis confirmed the composition, theoretical values: 35.65% of C, 2.76% of H and 6.40% of N; experimental values: 36.13% of C, 2.96% of H and 6.75% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-24 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-24 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results were recorded in table 2.
Example twenty-five
(1) Synthesis of manganese cobalt binary Metal catalyst Compound XMC-25 (completed under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and manganese compound MnCl 2 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr) 2 MnCl 2 . Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-25 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr) 2 MnCl] + [Co(CO) 4 ] - The yield was 86%. Elemental analysis confirmed composition, theoretical value: 47.37% of C, 4.34% of H and 10.04% of N; fruit of Chinese wolfberryAnd (4) checking the value: 47.35% of C, 4.33% of H and 10.08% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-25 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-25 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 2.
Example twenty-six
(1) Synthesis of manganese cobalt binary Metal catalyst Compound XMC-26 (done under inert atmosphere)
Weighing a certain amount of ligand C in a nitrogen atmosphere 5 H 4 N-2-CH = NiPr and manganese compound MnCl 2 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr)MnCl 2 . Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with normal hexane to obtain the compound XMC-26 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr)MnCl] + [Co(CO) 4 ] - The yield was 86%. Elemental analysis confirmed the composition, theoretical values: 38.12% of C, 2.95% of H and 6.84% of N; experimental values: 38.63% of C, 3.14% of H and 7.36% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-26 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-26 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing the sample injection valve, connecting the carbon monoxide steel cylinder, rapidly heating to 80 ℃, and simultaneously adjustingThe pressure of the joint system is 3.0MPa, the stirring speed is 800rpm, and the joint system is kept for 3 hours. After the reaction, the reaction vessel was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted and subjected to gas chromatography (the gas chromatogram is shown in fig. 1), and the results are recorded in table 2.
Example twenty-seven
(1) Synthesis of lanthanum cobalt binary Metal catalyst Compound XMC-27 (done under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and lanthanum compound LaCl 3 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr) 2 LaCl 3 . Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-27 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr) 2 LaCl 2 ] + [Co(CO) 4 ] - The yield was 80%. Elemental analysis confirmed composition, theoretical value: 39.02% of C, 3.57% of H and 8.27% of N; experimental values: 39.03 percent of C, 3.54 percent of H and 8.25 percent of N.
(2) Preparation of 3-hydroxy propionate by using XMC-27 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-27 1mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results were recorded in table 2.
Example twenty-eight
(1) Synthesis of lanthanum cobalt binary Metal catalyst Compound XMC-28 (done under inert atmosphere)
Weighing a certain amount of ligand C in a nitrogen atmosphere 5 H 4 N-2-CH = NiPr and lanthanum compound LaCl 3 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr)LaCl 3 . Then adding an equimolar amount of Na [ Co (CO) ] 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-28 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr)LaCl 2 ] + [Co(CO) 4 ] - The yield was 80%. Elemental analysis confirmed composition, theoretical value: 29.52% of C, 2.29% of H and 5.30% of N; experimental values: 30.17% of C, 2.54% of H and 5.76% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-28 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle to carry out N 2 After washing, sequentially adding XMC-28 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, connecting a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 2.
Example twenty-nine
(1) Synthesis of zirconium cobalt binary Metal catalyst Compound XMC-29 (done under inert atmosphere)
Weighing twice the amount of ligand C in nitrogen atmosphere 5 H 4 N-2-CH = NiPr and zirconium compound ZrCl 4 Placing the mixture into a Schlenk bottle, adding a toluene solvent, and stirring the mixture for 12 hours at room temperature to obtainTo (C) 5 H 4 N-2-CH＝NiPr) 2 ZrCl 4 . Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure, and washing with n-hexane to obtain the compound XMC-29 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr) 2 ZrCl 3 ] + [Co(CO) 4 ] - The yield was 71%. Elemental analysis confirmed composition, theoretical value: c39.74%, H3.64%, N8.43%; experimental values: 39.73% of C, 3.67% of H and 8.45% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-29 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle for N 2 After washing, sequentially adding XMC-29 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results were recorded in table 2.
Example thirty
(1) Synthesis of zirconium cobalt binary Metal catalyst Compound XMC-30 (done under inert atmosphere)
Weighing a certain amount of ligand C in a nitrogen atmosphere 5 H 4 N-2-CH = NiPr and zirconium compound ZrCl 4 Placing the mixture in a Schlenk bottle, adding a toluene solvent, and stirring the mixture at room temperature for 12 hours to obtain (C) 5 H 4 N-2-CH＝NiPr)ZrCl 4 . Then adding an equimolar amount of Na [ Co (CO) 4 ]Reacting for 8 hours, filtering and collecting filtrate, removing the solvent under reduced pressure and washing with n-hexane to obtain the compound XMC-30 with the molecular formula of [ (C) 5 H 4 N-2-CH＝NiPr)ZrCl 3 ] + [Co(CO) 4 ] - The yield was 71%. Elemental analysis confirmed the composition, theoretical values: 30.22 percent of C,h2.34%, N5.42%; experimental values: 30.90% of C, 2.47% of H and 8.87% of N.
(2) Preparation of 3-hydroxy propionate by using XMC-30 as catalyst (reaction completed under inert atmosphere)
Selecting a 300mL high-pressure reaction kettle for N 2 After washing, sequentially adding XMC-30 mmol, triethylamine additive 0.03mmol, ethylene oxide 100mmol and methanol 30mL, closing a sample injection valve, switching on a carbon monoxide steel cylinder, rapidly heating to 80 ℃, simultaneously adjusting the system pressure to 3.0MPa, stirring at the speed of 800rpm, and keeping for 3 hours. After the reaction, the reaction kettle was rapidly cooled to 0 ℃, slowly depressurized to normal pressure, the reaction solution was extracted, and subjected to gas chromatography, and the results are recorded in table 2.
Table 2: summary of catalytic results for examples seventeen to thirty
1mmol of catalyst; 0.03mmol of auxiliary agent; ethylene oxide EO 100mmol; 30mL of solvent; the stirring rate was 800rpm.
Example thirty-one
The reaction temperature for preparing the 3-hydroxy propionate by catalysis in twenty-five of the example is changed to 20 ℃, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example thirty-two
The reaction temperature for preparing the 3-hydroxy propionate by catalysis in twenty-five of the example is changed from 80 ℃ to 35 ℃, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example thirty-three
The reaction temperature for preparing the 3-hydroxy propionate by catalysis in twenty-five of the example is changed from 80 ℃ to 50 ℃, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example thirty-four
The reaction temperature for preparing the 3-hydroxy propionate by catalysis in twenty-five of the example is changed to 65 ℃, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example thirty-five
The reaction pressure of 3MPa for preparing the 3-hydroxy propionate by catalysis in twenty-five of the example is changed into 1MPa, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example thirty-six
The reaction pressure of 3MPa for preparing 3-hydroxy propionate by catalysis in twenty-five of the example is changed into 2MPa, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example thirty-seven
The reaction pressure of 3-hydroxy propionate prepared by catalysis in twenty-five of the example is changed to 4MPa, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example thirty-eight
The reaction pressure for preparing 3-hydroxy propionate by catalysis in twenty-five of the example is changed from 3MPa to 5MPa, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example thirty-nine
The reaction pressure for preparing 3-hydroxy propionate by catalysis in twenty-five of the example is changed from 3MPa to 6MPa, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example forty
The reaction pressure of 3MPa for preparing the 3-hydroxy propionate by catalysis in twenty-five of the example is changed into 7MPa, and other operation conditions are not changed. After the reaction, the reaction solution was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example forty one
The reaction pressure of 3MPa for preparing the 3-hydroxy propionate by catalysis in twenty-five of the example is changed into 8MPa, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example forty two
The reaction time for preparing 3-hydroxy propionate by catalysis in twenty-five of the example is changed from 3h to 2h, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example forty-three
The reaction time for preparing 3-hydroxy propionate by catalysis in twenty-five of example is changed from 3h to 4h, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example forty four
The reaction time for preparing 3-hydroxy propionate by catalysis in twenty-five of example is changed from 3h to 5h, and other operation conditions are not changed. After the reaction, the reaction solution was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example forty-five
The reaction time for preparing 3-hydroxy propionate by catalysis in twenty-five of example is changed from 3h to 6h, and other operation conditions are not changed. After the reaction, the reaction solution was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Example forty-six
The reaction time for preparing 3-hydroxy-propionate by catalysis in twenty-five of example is changed from 3h to 7h, and other operation conditions are not changed. After completion of the reaction, the reaction mixture was sampled by filtration and analyzed by gas chromatography (chromatogram shown in FIG. 2), and the results are shown in Table 3.
Example forty-seven
The reaction time for preparing 3-hydroxy propionate by catalysis in twenty-five of example is changed from 3h to 8h, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 3.
Table 3: EXAMPLES A summary of the catalytic results from thirty-one to forty-seven
1mmol of catalyst; 0.03mmol of auxiliary agent; ethylene oxide EO 100mmol; 30mL of solvent; the stirring rate was 800rpm.
Example forty-eight
The reaction solvent methanol for preparing the 3-hydroxy propionate by catalysis in twenty-five of the example is changed into ethanol, and other operation conditions are not changed. After the reaction, the reaction solution was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 4.
Example forty-nine
The reaction solvent methanol for preparing 3-hydroxy propionate by catalysis in twenty-five of the example is changed into propanol, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 4.
Example fifty
The reaction solvent methanol for preparing the 3-hydroxy propionate by catalysis in the twenty-five embodiment is changed into butanol, and other operation conditions are not changed. After the reaction, the reaction solution was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 4.
Example fifty one
The reaction solvent methanol for preparing the 3-hydroxy propionate by catalysis in twenty-five of the example is changed into cyclopentanol, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 4.
Example fifty two
The reaction solvent methanol for preparing the 3-hydroxy propionate by the catalysis of the dodecafifteen in the example is changed into cyclohexanol, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 4.
Example fifty three
The reaction material ethylene oxide for preparing 3-hydroxy propionate by catalysis in twenty-five of the example is changed into propylene oxide, and other operation conditions are not changed. After the reaction, the reaction solution was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 4.
Example fifty four
The reaction raw material ethylene oxide for preparing the 3-hydroxy propionate by catalysis in twenty five of the example is changed into butylene oxide, and other operation conditions are not changed. After the reaction, the reaction mixture was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 4.
Example fifty five
The reaction raw material ethylene oxide for preparing the 3-hydroxy propionate by catalysis in twenty five of the example is changed into cyclohexene oxide, and other operation conditions are not changed. After the reaction, the reaction solution was filtered, sampled and analyzed by gas chromatography, and the results are shown in Table 4.
Table 4: summary of catalytic results for examples forty-eight to fifty-five
1mmol of catalyst; 0.03mmol of auxiliary agent; 30mL of solvent; the stirring rate was 800rpm.
Claims (14)
1. A binary metal catalyst represented by [ (C) 5 H 4 N-2-CH＝NR) m ML n ] + [Co(CO) 4 ]-, where m =1 or 2;
when m =2, the binary metal catalyst has a structure represented by general formula (A),
when m =1, the binary metal catalyst has a structure represented by general formula (B),
wherein M is selected from Rh, cr, al, ti, mn, la and Zr;
each R is independently selected from C 1-12 Straight or branched alkyl, C 1-12 Heteroalkyl group, C 3-12 Cycloalkyl radical, C 3-12 Heterocycloalkyl or C 6-10 Aryl, wherein said C 1-12 Straight or branched alkyl, C 1-12 Heteroalkyl group, C 3-12 Cycloalkyl radical, C 3-12 Heterocycloalkyl or C 6-10 Aryl being optionally substituted by halogen, hydroxy, amino, cyano, C 1-6 Alkyl radical, C 1-6 At least one of alkoxy groups is mono-or poly-substituted;
l is selected from hydrogen, -C = O, halogen, pseudohalogen, C 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 1-6 Alkanethiol, C 6-10 Aryl radical, C 6-10 Heteroaryl, amino, hydroxy, C 1-6 Carboxyl group, sulfonic acid group, C 1-6 Alkylsulfonic acid group, or acetylacetonato group, wherein said C 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 1-6 Alkanemercapto group, C 6-10 Aryl, amino, C 1-6 Carboxyl group, sulfonic acid group, C 1-6 Alkylsulfonic acid group, acetylacetone group optionally substituted by halogen, hydroxy, cyano, C 1-6 Alkyl radical, C 1-6 At least one of alkoxy, amino and trimethylsilyl is mono-substituted or polysubstituted;
n represents the number of L and is an integer of 0 to 3.
2. The binary metal catalyst according to claim 1, wherein each R is independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diisopropylphenyl, 2, 6-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, 2,4, 6-triisopropylphenyl, 2,4, 6-tri-tert-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, thienyl.
3. The binary metal catalyst according to claim 1, wherein L is selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, butyl, trimethylsilylmethyl, phenyl, benzyl, methoxy, ethoxy, phenol, formate, acetate, dimethylamino, diethylamino, diisopropylamino, di-t-butylamino, bis (trimethylsilyl) amino, acetylacetonate, hydroxyl, sulfonic acid, methylsulfonic acid, and trifluoromethylsulfonic acid.
4. A binary metal catalyst selected from the group consisting of:
5. a method for preparing the binary metal catalyst of any one of claims 1-3, comprising:
reacting compound (C) 5 H 4 N-2-CH＝NR) m ML n+1 And Na [ Co (CO) 4 ]And (3) reacting in a first organic solvent to remove LNa, thereby obtaining the binary metal catalyst.
6. The method according to claim 5, wherein the first organic solvent is at least one selected from the group consisting of alkanes, aromatic hydrocarbons, heterocyclic alkanes, halogenated hydrocarbons, ethers, and amines.
7. The method according to claim 6, wherein the first organic solvent is at least one selected from the group consisting of benzene, toluene, xylene, tetrahydrofuran, diethyl ether, hexane, heptane, chloroform, methylene chloride, triethylamine and methylphenylamine.
8. Use of the binary metal catalyst of any one of claims 1-4 in the catalytic preparation of a 3-hydroxypropionate ester.
9. A method for preparing a 3-hydroxypropionate ester, comprising the steps of:
reacting a reaction system comprising the bimetallic catalyst of any one of claims 1-4, an adjunct, an alkylene oxide, carbon monoxide, an organic alcohol, and optionally a second organic solvent, to produce a 3-hydroxypropionate ester;
wherein the binary metal catalyst is prepared from a compound (C) 5 H 4 N-2-CH＝NR) m ML n+1 And Na [ Co (CO) 4 ]In-situ reaction in a reaction system or pre-synthesis;
the auxiliary agent is an alkaline substance;
the second organic solvent is at least one selected from alkane, ether, tetrahydrofuran, 2, 6-oxygen ring, aromatic solvent and halogenated hydrocarbon.
10. The method according to claim 9, wherein the molar amount of the auxiliary is 0.01 to 10% of the molar amount of the catalyst.
11. The method of claim 9, wherein the second organic solvent is selected from at least one of pentane, hexane, cyclohexane, diethyl ether, tetrahydrofuran, benzene, toluene, and dichloromethane.
12. The production method according to claim 9, wherein the organic alcohol is at least one selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, and benzyl alcohol; and/or
The alkylene oxide is at least one selected from ethylene oxide, propylene oxide, butylene oxide and cyclohexene oxide; and/or
The auxiliary agent is selected from inorganic carbonate, main group metal salt of organic alcohol or phenol or carboxylic acid, main group metal amino compound, main group metal alkoxy compound and main group metal hydride.
13. The method of claim 12, wherein the auxiliary agent is at least one selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, sodium ethoxide, sodium phenolate, sodium acetate, diethylamine, triethylamine, and diethanolamine.
14. The production method according to any one of claims 9 to 13, wherein the reaction conditions are as follows:
the reaction temperature is 0-250 ℃; the reaction pressure is 0.1-60 MPa; the reaction time is 1 to 50 hours.
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